Process of manufacture of diphenylenediketones from anthracene compounds



Patented May 15, 1923.

UNITED, STATES PATENT OFFICE.

GUSTAV PETERS, OF WORMS, GERMANY.

PROCESS OF MANUFACTURE OF DIPHENYLENEDIKETONES FROM ANTHRACENE COMPOUNDS. I v

No Drawing.

To all whom it may concern:

Be it known that I, GUs'rAv PETERS, a citizen of Germany, residing at Worms, Germany, have invented certain new and useful Improvements in Processes of Manufacture of Diphenylenediketones from Anthracene Compounds (for which I have filed applications in Germany, filed May 18, 1918; Dec. 27, 1919; Austria, filed June 18, 1919; Hungaria, filed July 8, 1919; Czechoslovakia, July 21, 1919; Switzerland, May 17 1919, Patent No. 84262; Denmark, June 11, 1919; Sweden, May 14, 1919, Patent No; 48662; Norway, June 11, 1917, Patent No. 31823; Netherlands, May 17, 1919, Patent No. 5401), of which the following is a specification.

The present process refers to the manufacture of diphenylenediketones from anthracene compounds by oxidizing agents.

The present process consists in causing oxygen to act on anthracene compounds in the presence of oxygen carriers, i. e. oxygen containing substances which give 011' oxygen easil and combine easily with oxygen. As suita le oxygen carriers I have found especially nitrogen oxygen compounds, nitrous oxide, nitric oxide, nitrosylchloride, nitrogen trioxide, nitrogen peroxide, nitrogen pentoxide or nitric acid. I may use a single nitrogen oxygen compound .or mixtures of several nitrogen oxygen compounds. I ma use the nitrogen oxygen compounds in a mixture with other catalysts as metal oxides, for instance cobalt, nickel, iron,'manganese oxides or such like or metal salts, for instance sulphates, nitrates, acetates, propionates of cobalt, nickel, iron, manganese or such like. The rocess'is carried out by suspending or. v issolving the anthracene compounds in aliphatic organic acids, as acetic acid, especially acid which 'is concentrated, or free of water, as so called glacial acetic acid. I may add indifferent nonacid diluents for instance dichlorbenzene,

nitrobenzen'e.

In case aliphatic acids are used the tempgrature is preferably maintained below the iling point of the aliphatic acids in order to eliminate gaseous products as for instance the nitrogen oxygen compounds.

suitably heating the mixture,

der pressure. As oxygen if desired un- I ing point, 276 The actlon of oxygen is carriedout by- Application filed August 9, 1921. Serial No. 491,023.

containing gases or vapours, as for instance air, liquefied and afterwards gasified air, which may have a higher proportion in oxygen than corresponding to the ordinaryair or such like. I may prepare anthraquinone by means of the present process from anthracene, oxanthranol, monochloranthracene, dichloranthracene or I may prepare derivatives of the anthraquinone as anthrai vmixed in a boiler with 500-1000 kilos of concentrated acetic acid at about 90 vC.

a small proportion of fuming nitric acid is added and oxygen is introduced under pressure. The necessary proportion of oxygen is rapidly absorbed and after about 3-5 hours the oxidation is complete.

2. 50 kilos of anthracene are stirred in a boiler with 500 kilos of concentrated acetic acid at 8090 C. and 100 grams of cobalt nitrate, while oxygen containing a small percentage of nitrous gases is introduced. The oxidation is finished in some hours. In like manner derivatives such as anthracene sulphonic acids can be oxidized to corresponding quinone compounds. l

3. 50 kilos of anthracene of per cent strength are heated to 90 C. in a closed vessel with 250 kilos of propionic acid, while. stirring, oxygen is now introduced while simultaneously drop ing in N0 or passing in gaseous N0 The oxygen is v1olently absorbed and the anthracene becomes ani After some hours the reacacetic acid to which 20 per cent'water has been added. Yield, 95-98 per cent. Melt-' per cent.

I claim:

'105 i 0., degree of purity, 92-95 1. Process for manufacturing diphenylene diketones which comprises, heating anthr'a- 1 cene compounds with free oxygen the presence of an or anic solvent and a relatively small quantity of an oxy en carrier.

2. Process for manufacturing diketones which comprises heating anthracene compounds with free oxygen in the presence of an organic acid, and a nitrogenoxygen compound, said nitrogen oxygen compound being insuflicient in quantity to accomplish the oxidation.

3. Process for manufacturing diphenylene diketones which comprises heating anthracene with free oxygen in the presence of a relatively small quantity of an oxygen carrier, ,an organic solvent and an indifferent diluent. i

4. Process of manufacturing diphenylene diketones which comprises heating anthraiphenylene' cene with free oxygen in the presence of an aliphatic acid, an oxygen carrier, and a catalytic body.

. 5. Process of manufacturing diphenylene diketones which comprises heating anthracene dissolved in an aliphatic acid contain ing an indifferent diluent with free oxygen in the presence of an oxid of nitrogen and a metaloxid catalyst.

6. Process of manufacturing diphenylene diliet-ones which comprises heating anthracene with free oxygen in the presence of nitrogen oxygen compounds and a metal compound catalyst.

In testimony whereof I hereunto my signature.

GUSTAV rnrnns. 

